Composition toxic to lower forms of



Reissued a. 4, 1938 V R 20,869

UNITED STATES PATENT OFFICE 20,869 COMPOSITION Toxllgg) LOWER FORMS OF Euclid W. Bousquet, Wilmington, George D. Graves, Holly Oak, and Paul L. Sa berg, Carrcroft, Del., assignors, by mesne assignments, to E. L du Pont de Nemours & Company, Wil- No Drawing. Original No. 2,030,093, dated February 11, 1936, Serial No. 649,448, December 29, 1932. Application for reissue October 1, 1937, Serial No. 166,858 v 8 Claims. (Cl. 167-422) The present invention refers to compositions best used in the form of aqueous emulsions in toxic to lower forms of life which comprise orthe presence of the usual emulsifying and spreadganic compounds containing in their molecule a ing agents, such as sulfonated vegetable, animal straight carbon chain of 12 carbon atoms, subor mineral oils, soaps, alkylated hydrocarbon sulstituted particularly at least at one of its end fonic acids, etc.

carbon atoms by a negative atom or a group con- We also found that the toxicity of the ntaining such a negative atom, said carbon atoms dodecyl group persists in a number of other also carrying hydrogen. By negative atom We derivatives in which it is combined with other mean a non-metallic element included in groups elements and groups. These toxic n-dodecyl V, VI, and VII of the periodic system of elements, derivatives can be represented by the type for- 10 in other words, the substituents consist of or mula CH3(CH2)11X in which X is a subcomprise nitrogen, phosphorous, oxygen, sulfur, stituent as characterized by the following four selenium, tellurium or a halogen. definitions:

These derivatives of n-dodecane (CizHzsl are all 1. X= OH, SH, SeH, IeH; 0R, SR, SeR, TeR. toxic to lower forms of life, particularly fungi, in- R being an organic radical.

15 sects and more specifically soft bodied insects, This includes n-dodecyl alcohol and its ethers 15 A and we attribute this characteristic toxicity to as well as their sulfur, selenium and tellurium the hydrocarbon chain irrespective of the subanalogs; also esters of organic sulfur acids as stituents described above which affect the toxicity xanthates, etc. only in a gradual manner. 2. X=Inorganic acid radical. 2 n-Dodecyl alcohol or n-dodecanol This includes n-dodecyl chloride, bromide,

fluoride, cyanide, sulfate, nitrate, phosphate,

C M Q eyanate, sulfonate, etc. has become technically available by various syn- 3. 0 CC acyloxy radical thetic methods. It is quite eiiective for control- Thls Includes the orgamc ndodecyl esters such 25 ling soft bodied insects, such as aphids, thrips, etc. g g' formate chloroacetate' benzoate n-Dodecyl amine and its substitution products p a a e are similarly toxic to insects arid can be used X=NR1R2 wglere R1 and R2 may be hydrogen for controlling and combating lower forms of life. or 3 radlcal' 3o Esters of n-dodecyl alcohol with organic or This Includes nudodecyl ammes mdodecyl inorganic acids, particularly those containing sul- "t ndodecy guanidine' mdodecyl thiourea' fur and/or nitrogen are even more effective as QP dlthlocarbamate as well as insecticides than the straight n-dodecyl alcohol. salts;

In the case of the esters of or polybasic The toxicity of these n-dodecyl derivatives also acids with mdodecfl alcohol, We may use the persists if the n-dodecyl chain carr es a negative 5 neutral esters but We prefer to use the partial Substltuent such as C11 Bog-H Yvmch does n dodecyl mercaptide, sodium n-dodecyl phthalate obtained the hydrgenafin P 6900mm or 40 are examples of water Soluble salts f partial its free fatty acids, and the derivatives obtained n-dodecy] esters which can be used in this from this crude alcohol. This product contains m n largely n-dodecyl alcohol with small amounts of.

The n-dodecyl halogenids are regarded as the higher or 1 from n-octyl i 45 esters of n-dodecyl alcghol th hydmhalogen cetyl alcohol, but the insecticidal value of such acids. These esters as well as the esters or nmiXtureS of alcohol Corresponding derivatives dodecyl alcohol with monobasic acids are subis dependent primarily on the content of nstantially water insoluble. These, as well as dodecyl derivatives.

0 other water insoluble n-dodecyl derivatives, are Among the large number of toxic n-dodecyl 5O 2 Y ao,eoe

derivatives exemplified above we cite the followondary alcohols or their derivatives containing ing, which are of great merit for controlling carbon chains ofless than 12 or more than 12 insect pests thriving on vegetable life. and some carbon atoms are considerably less eflective than of the results obtained by their use. n-dodecyl alcohol or its derivatives. Thus, for

- instance, while potassium lauryln-dodecyl xans 7 I p thate at 0.2% concentration with sulionated Compo o 1mct fi nsh oil gave a 99-100% control on aphids, the 9 control with potassium n-octadecyl xanthate was only 35-40%. n-vodwvwwholiii-m g gg ffi B gfgg g j M we also found that mixtures of alcoholscon- 10 (0.25%). m ataining from 10 to 13 carbon atoms consisting P mainly of secondary alcohols as produced from. h 5 if t a a 00.0 romiumndodwylm Egg 2:11 unsaturated petroleum hydrocarbons have very Potassium Modecymnmm "30: "do 9 low toxicity toward lower forms of life. such as 15 (0.1%). fungi and insects. 15

tififiieiiiiiewfi 'l aat'ast $5 r y o il flsfap 1. A composition toxic to lower forms of life comprising as the active toxic ingredient a subo o. 5 ii t a o t ass n Dodges" mom H 2%) iiga o il $11 13: stance selected from the group or substances conmnadecyl dmhymmmw Blackchrw BM sisting of n-dodecyl alcohol, n-dodecyl esters and go ew (0.1%). a n t h e n-dodecyl amines and their salts.

31a 2. A composition toxic to lower forms of life n'DodBcyI alcohol with 10% None Tobacco 100. comprising as an active toxic ingredient an ni thflpsdodecyl ester. 3. A composition toxic to lower forms of life as our no v61 insecticides can also used m fly comprising as the active toxic ingredient an ndodecyl ester of an organic acid. sprays, preferably in combination with petroleum hydrocarbons such as kerosene. Their t' ig zz g gfif g ig g i i g 1 me toxic action on the common house fly is very satmdodecm xanthate g e an an 80 isfactory. In three comparable experiments we 1 have for instance sprayed flies with kerosene, A composition toxic to lower forms of me comprising as the active toxic ingredient a comwith kemsene containing pyrethmm and with pound containing a straight chain of 12 carbon kerosene containing 10% n-dodecyl alcohol. The atoms in which one of the end atoms carries by flies were kept under observation for 24 hours. dream and a negative nommetamc atom 85 All of the flies sprayed with kerosene recovered. A composition a to lower form-s Me whereas the pyrethmm kerosene spray gave comprising as the active toxic ingredient a commortality and the n-dodecyl-alcohol kerosene pound containing a straight chain, 12 carbon spray gave mortality atoms in which one of the end carbon atoms car- The outstanding advantage of our new ini secticides is their high toxicity in low concentraz fi g g ggg gs f f z a %fi g 3:333:

tions and their harmlessness to plant life. We 5 stem of elements have found that n'dodecyl compounds and 'l. A composition toxic to lower forms of life rivatives are unique in this respect. In view of c the fact that ethyl alcohol can be applied in 100% 8 35 :2 331; :3 sf an f fi q 2 than giving 8. A composition toxic to lower forms of life a p e 8 con t 13 sun) 5mg that n'dodecyl comprising as an active toxic ingredient a comrtlfhol gives excellent control at 0.2% ooncentrapound selected f o the group con'sisflng of on. Similarly, other long carbon chain alcohols n dad-my1 amines and their salts' and their derivatives have only a very mild toxic EUCLID w. noosonn'r.

eflect towards insects and other lower forms of GEORGE D. GRAVES.

life. We found, for instance, that primary or sec- 0 PAUL L. SALZBERG. 

